Resinous compositions



@atented wee. 2, i9

" era RESHNQEIS UQLWQSK'EKONS William a. more, Wilmington, Delt, assignor to E. ii. du Pont de Nemours & Eompany, Wilmington, Deb, a corporation of Delaware No Drawing. ppiicatiom January 4, EMS,

SerialfNo. 571,3'22

'1 Claims. (03. sec-i2) i 2 This invention relates to improvement in resin- This invention is illustrated further by means ous compositions, and more particularly to an of the following example. improved adhesive composition adapted for use Example-A mixture containing ids grams of in the manufacture of laminated materials. hexamethylenedialnine dissolved in 200 cc. of

An object of this invention is to provide an 55 methanol was heated at the boiling point in areadhesive composition which may be readily preaction vessel equipped with a reflux condenser. pared from inexpensive and available materials. A solution containing 30.4 grams of carbon bisuiand which is of value in the manufacture of high fide in 100 cc. of methanol was introduced with quality hot-pressed laminated objects, particur pi tirrin When about half of the carbon larly plywood. Another object is to provide hotdisulflde solution had been added a white precippressed plywood which has excellent shear tate pp h total on is fid 11- strength even after prolonged contact with boiltion was introduced over a P d of a ou 10 ing water. Yetanother object is to prepare imminutes- The resulting re was 6 0 6111 and proved resinous compositions which yield cured fi r h fil er cake thus obtained was resins upon the application of heat, even in the 15 washed with methanol and was allowed to y in absence of added catalysts. the air. A portion of this dry material (10 These and other objects are accomplished in grams) was dissolved in 40 rams of pyridin y accordance with the invention by providing aheating at reflux temperature for one 0" composition containing as its essential ingredi-' Polymerization u e s s evidenced by the cuts, a diamine, such as polyinethylenediamine of evelution 0f fi To t s so tion was added the formula NH2(CH2) nNHz, n being an integer 5.6 grams o 4 solution containing 5 by Weight from 3 to 10, carbon bisulfide and formaldehyde. psraformaldehyde sso v d in methanol. Re- It has been discovered, in accordance with this infilming Was nued for /2 hour. The refluxvention, that a hexamethylenediamine-carbon 8 mixtulswas added to 6 t r of d bisulfide reaction product, modified by treatment the precipitated pr du t as s parat d from the with formaldehyde,-may be employed as a plysupernatant liquid. This precipitated material wood adhesive in the manufacture of hot-pressed Was then dispersed in ater in the form of a plywood which meets United States Army and moist paste- 4 The Paste s pp d to the s Navy requirements as set forth in Specification faces of birch veneers at the e of 25 r ds AN-NN-P-511b for aircraft plywood, of solids per thousand square feet of glue line In one specific embodiment, thi inv t area, and the coated veneers were laminated by may be practiced by treating about 1 mol of heating at a temperature of 145 to 150 C. under hexamethylenediamine in an organic solvent p sur o 200 pounds p q e c f 20 with about 1 mol of carbon bisulfide at a temminutes. The resulting p y o d had a dry'sheal perature of about to C., and thereafter 5 st ength of 640 pounds per square inch, and a polymerizing the resulting reaction product in Wet s e strength (after being subj to the the presence of a solvent such as pyridine, and a tion of boiling water for 3 hours) of 580 P0111165 treating the polymerized product with about 1 F square inchmol of formaldehyde, preferably in alcoholic so- The diamines which may be used in the praclution. The resulting solution of formaldehydetics of this invention include trimethylenediamodified hexamethylenediamine-carbon bisulmine, tetramethylenediamine, 1,3 diaminobufide reaction product is admixed with a relativetane, pentamethylenediamine, alpha-methyl penly large volume of water whereby a precipitate is tamethylene dismine, y e d fi e. formed. The, precipitate, thus obtained, is a res- 5 t y diamine, and the like. Ethyl nein which cures when heated to a temperature of diamine generally gives se o unsatisfactory reabout 80 to 150 C. In standard tests, plywood, sults, due to the formation of cyclic monomeric prepared by coating veneers with an aqueous compounds. The reaction between carbon disulpaste of the thermosetting resin and pressing the fide and the diamine initially yields a salt, which coated veneers together at a temperature of 50 on further heating preferably at about 80 to to 175 (3., preferably about to 0., under 250 C. is polymerized with liberation of hydropressure of about 30 to 300 pounds per square gen sulfide. During the polymerizationthe reacinch, has a dry and wet strength well above the tion product becomes readily soluble in pyridine. minimum (dry, 390 pounds per square inch; wet, This polymeric product reacts with formaldehyde 290 pounds per square inch) set forth in Specifito yield a thermosetting resin, as described in the cation AN-NN-P-511b. example.

One of the advantages of the adhesives of this 7 invention is that they may be cured in the absence of acidic or alkaline catalysts. Such catalysts may be employed, but they are generally unnecessary. Another advantage of the adhesives of this invention is the remarkably hich bond strength obtained even after the plywood containin this adhesive has been subjected to the action of boilingwater.

The improvements in resinous compositions disclosed herein have been described with particular referenceto the formaldehydereaction.

products as adhesives for plywood. The compo- .sitions ofthe invention are likewise very valuable 1cmto those who are skilled in the art. Accordingly I do not limit myself-except as set forth in the'following claims.

I claim:

1. A thermosetting adhesive composition, adapted for use in manufacturing plywood, comprising an aqueous paste containing formaldehyde-modified hexamethylenediamine-carbon bisulfide reaction product.

2. A process which comprises reacting hexamethylenediamine in a solvent with carbon bisulfide at a temperature in the range of 50 to 80 0., separating the resulting reaction product from thesupernatant liquor, heating the said product at about 80 to 250 C. wherebypolymerization occurs, reacting the resultant product with formaldehyde in alcohol solution, whereby a formaldehyd'e-modified hexamethylenediamine-carbon bisulfide reaction product is obtained.

3. A process which comprises reacting hexamethylenediamine in a solvent with carbon bis sulfide at a temperature in the, range of 50 to 80 0., separating the resulting reaction product from the supernatant liquor, polymerizing the said reaction product by heating in the presence of pyridine, reacting the resulting mixture .with

formaldehyde in methanol solutiomwhereby a] solution of formaldehyde-modified hexamethylenediamine-carbon liisulfiiie reaction product is obtained.

4. A process which comprises reacting at a temperature of 50 to 80 0. about 1 mol equivalent of hexamethylenediamine with a methanol solution of about 1 mol equivalent of carbon bisulflde, whereby a hexamethylenediamine-carbon bisulfide reaction product .is obtained, separating the said hexamethylenediamine-carbon bisulflde reaction product from the supernatant liquor, polymerizing the said product at 80 to 250 C., and treating the resulting product with about 1 mol equivalent of formaldehyde in methanol solution, whereby a formaldehyde-modified hexamethylenediamine-carbon bisulfide reaction product is produced.

5. A thermosetting resinous composition comprising formaldehyde-modified polymethylenediamine-carbon bisulfide reaction product, said polymethylenediamine having the formula NH: (CH2) "NH:

REFERENCES CITED The following references are of recordin the file of this patent:

UNITED STATES PATENTS Number Name Date 2,271,744 Nevin Feb. 3, 1942 2,320,817 D'Alelio June 1, 1943 I composition, 7 

